Dry active oxygen technology

ABSTRACT

Active oxygen compounds, such as equilibrium peroxycarboxylic acid compositions are incorporated within an adsorbed outer layer of hydrophobic particulate component that remains undissolved from the active oxygen component. The dry powder compositions containing the active oxygen compounds provide a stable, controlled release composition having various applications of use. Beneficially, the dry powders delivering active oxygen compounds are low or no odor compositions and do not require the use of personal protective equipment for persons handling the compositions.

FIELD OF THE INVENTION

The invention relates to the use of dry water technology for activeoxygen compounds, such as hydrogen peroxide, peracid compositions suchas peracetic acid, and the like. In particular, the compositions includean active oxygen component in a liquid droplet or aqueous formsurrounded by a shell component of hydrophobic nanoparticles thatremains undissolved from the liquid droplet of the active oxygencomponent. Methods of delivering the same active oxygen compounds arealso provided that have controlled release and/or distribution of theactive oxygen components of the composition. Beneficially, the drypowders delivering active oxygen compounds are low or no odorcompositions.

BACKGROUND OF THE INVENTION

Compositions including bleaching and other active oxygen oxidant agentsare commonly formulated into powder or granule compositions. There isalso interest in marketing and using such products in various the liquidforms. For example, detergent particle cleaning compositions can beformulated into liquid compositions having particulate componentssuspended therein. However, stability concerns are often presented bysuch formulations, such as disclosed in U.S. Pat. Nos. 7,435,714 and7,588,697, which are incorporated herein by reference in their entirety.However, many of these compositions have various stability limitations,particularly when incorporating active oxygen components into thecompositions, such as peroxycarboxylic acids (e.g. peracetic acid).Peracid compositions, namely peroxycarboxylic acid compositions, exhibituseful antimicrobial and bleaching activity and therefore would bedesirable to formulate into stable powder or granule compositions (e.g.,U.S. Pat. Nos. 5,200,189, 5,314,687, 5,409,713, 5,437,868, 5,489,434,6,674,538, 6,010,729, 6,111,963, and 6,514,556, each incorporated hereinby reference in its entirety).

Various applications of “dry water” technology have extended to use informulating compositions using coated bleach or other active oxygenliquid compounds. Description of such “dry liquid” (or “dry water”)compositions was originally disclosed for example, by DegussaCorporation, Degussa Corporation Manuscript “Dry Water-a formulationprinciple with hydrophobic Aerosil®,” which is herein incorporated byreference in its entirety. Methods of using the technology to deliverwater alone in a dry powder composition is disclosed by Forny et al.,Powder Technology 171 (2007) 15-24, which is also incorporated herein byreference in its entirety.

U.S. Pat. No. 7,718,592, which is incorporated herein by reference inits entirety, discloses the use encapsulation of a particulate byanother particle, which is distinct from “dry water” technology.Instead, “dry water” technology includes a droplet of liquid surroundedby hydrophobic nanoparticles on the surface of the droplet to afford anapparent powder even while the starting droplet remains in a liquidstate. U.S. Publication Nos. 2010/0009889 and 2005/0233900, each ofwhich are herein incorporated by reference in their entirety disclosethe use of “dry water” technology with a hypochlorite solution innerdroplet.

There is a need for dry water technology that provides a means ofdelivering (as a powder) a form of a liquid active oxygen solution whichis only slightly reduced in concentration relative to the startingliquid. These and other limitations in the art are overcome by thepresent invention.

Accordingly, it is an objective of the claimed invention to develop dryactive oxygen compositions that include a diphasic composition includingan aqueous or liquid active oxygen component which has an adsorbed layerof a hydrophobic silica component, which is at least 80% of the startingliquid active oxygen component by weight; preferably at least about 90%.

A further object of the invention is to develop more stable dry-to-touchpowder compositions containing an aqueous or liquid active oxygenoxidant within the compositions.

A still further object of the invention is to provide kits for use ofthe dry active oxygen compositions.

BRIEF SUMMARY OF THE INVENTION

In an embodiment, the present invention provides a dry active oxygencomposition including an aqueous active oxygen component and ahydrophobic component adsorbed to the outer layer of droplets of saidactive oxygen component. In an aspect the dry active oxygen compositionforms a flowable, dry-to-touch powder formed by an adsorbed outer layeronto the liquid or aqueous droplets of the aqueous active oxygencomponent by the hydrophobic component which does not dissolve withinthe aqueous component for a period of time greater than at least 24hours.

In a further embodiment, the present invention provides a kit comprisinga sealed container, a dry active oxygen composition comprising anaqueous active oxygen component and a hydrophobic component adsorbed tothe outer layer of droplets of said active oxygen component, andinstructions for application of use.

In a still further embodiment, the present invention provides a methodof using a dry active oxygen composition including combining an aqueousactive oxygen component, and a hydrophobic nanoparticle component toform a composite of the hydrophobic nanoparticle component adsorbed ontothe outer layer of droplets of liquid that is in the form of a flowable,dry-to-touch powder. The method also includes applying the dry activeoxygen composition to a surface in need of treatment or storing the dryactive oxygen composition within a sealed container for subsequentapplication to a surface in need of treatment. Optionally, the sealedcontainer may contain a venting device as a safety feature.

In certain aspects, the dry active oxygen compositions are producedusing an aqueous solution of peroxycarboxylic acids, sulfonatedperoxycarboxylic acids, hydrogen peroxide and/or other active oxygenoxidants. In certain aspects, the dry active oxygen compositions areproduced using a silica hydrophobic component, preferably wherein thesilica component is not an alkali metal silicate, and wherein saidsilica component is a hydrophobically modified silica having at leastabout 30% of the hydroxyl groups of said silica modified with a silaneto increase hydrophobicity. In certain aspects, the ratio of activeoxygen component to hydrophobic component is from about 80:20 to about97:3.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross-sectional view of an embodiment of the compositedry active oxygen composition 10 of the present invention showing atleast one active oxygen component 11 within an encapsulate, hydrophobicshell component 12.

FIGS. 2-4 show graphs set forth in Example 4 demonstrating thethermostability of the active oxygen compositions formulated into thedry powder compositions according to embodiments of the invention.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The embodiments of this invention are not limited to particular dryactive oxygen delivery compositions and methods of use thereof, whichcan vary and are understood by skilled artisans. It is further to beunderstood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form. Numeric ranges recited within the specificationare inclusive of the numbers defining the range and include each integerwithin the defined range.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism. For the purpose of this patent application, successfulmicrobial reduction is achieved when the microbial populations arereduced by at least about 50%, or by significantly more than is achievedby a wash with water. Larger reductions in microbial population providegreater levels of protection.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25±2° C., against several test organisms.

As used in this invention, the term “sporicide” refers to a physical orchemical agent or process having the ability to cause greater than a 90%reduction (1-log order reduction) in the population of spores ofBacillus cereus or Bacillus subtilis within 10 seconds at 60° C. Incertain embodiments, the sporicidal compositions of the inventionprovide greater than a 99% reduction (2-log order reduction), greaterthan a 99.99% reduction (4-log order reduction), or greater than a99.999% reduction (5-log order reduction) in such population within 10seconds at 60° C.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the performance of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt-%. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt-%.

As used herein, the term “sulfoperoxycarboxylic acid,” “sulfonatedperacid,” or “sulfonated peroxycarboxylic acid” refers to theperoxycarboxylic acid form of a sulfonated carboxylic acid. In someembodiments, the sulfonated peracids of the present invention aremid-chain sulfonated peracids. As used herein, the term “mid-chainsulfonated peracid” refers to a peracid compound that includes asulfonate group attached to a carbon that is at least one carbon (e.g.,the three position or further) from the carbon of the percarboxylic acidgroup in the carbon backbone of the percarboxylic acid chain, whereinthe at least one carbon is not in the terminal position. As used herein,the term “terminal position,” refers to the carbon on the carbonbackbone chain of a percarboxylic acid that is furthest from thepercarboxyl group.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Compositions

While an understanding of the mechanism is not necessary to practice thepresent invention and while the present invention is not limited to anyparticular mechanism of action, it is contemplated that, in someembodiments, the delivery of active oxygen components is provided in adry liquid (or solid liquid) droplet formulation as a result of anunabsorbed, inner aqueous or liquid component in contact with anadsorbed layer (e.g. outer layer) of a hydrophobic particulatecomponent. The compositions may be referred to herein as dry liquids,dry powders, solid liquids or the like. In an aspect, the compositionsinclude a hydrophobic particulate shell comprised of undissolvedparticulate components surrounding a liquid or aqueous dropletcontaining an active oxygen component. In some aspects, the nature ofthe interaction between the hydrophobic particulate shell and the activeoxygen containing liquid or aqueous droplet therein, may be a variety ofcohesion forces allowing the adsorbed outer layer, such as van derWaals. In an aspect of the invention, the active oxygen component is anaqueous solution or suspension of at least an oxidant and a stabilizingcompound. In the various aspects of the invention, the dry powderdroplets do not result in droplet coalescence.

In an aspect of the invention the compositions include a dry liquidcomposition having a composite aqueous, active oxygen compound withshelf stability. In preferred aspects, the dry liquid compositions maybe provided in a sealed container to prevent the evaporation and/ordisintegration of the composition into an aqueous composition.Preferably, the dry liquid compositions within a sealed container(optionally containing a venting safety feature) have a shelf-stabilityof at least about 2 to 6 months, preferably at least about 6 to 12months. The stability of the compositions upon exposure to ambientconditions will vary depending on such ambient conditions, including forexample, temperature and humidity. In an aspect, the dry liquidcompositions will convert into a liquid composition (having hydrophobicshell components contained therein) promptly upon exposure to shearforce that disrupts the adsorbed layer of the hydrophobic shellcomponent.

Without being limited to a particular theory of the invention, thepresent invention is distinct from prior art references withencapsulated compositions. Encapsulated compounds have asolid/particulate encapsulated by another solid/particulate. Distinctly,the present invention discloses a layer of hydrophobic nanoparticlesadsorbed (yet not encapsulating) onto the outer surface of a liquid oran aqueous droplet. Notably, the droplet according to the inventionremains in a liquid state even though the composite of the droplet(having the adsorbed particulate layer) is a powder.

Hydrophobic Shell Component

The compositions according to the invention include a hydrophobic shellcomponent. The hydrophobic shell component may also be described as anadsorbed layer of hydrophobic particulate components, which may bereferred to generally as a hydrophobic particulate component. Thehydrophobic particulate component according to the invention is simply alayer of particulates floating on the surface of a droplet of liquid.

In an aspect, the hydrophobic particulate portion is made up of smallparticles or nanoparticles suitable for adsorbing to the active oxygencomponents of the compositions. In some aspects, the hydrophobicparticulate component forms a porous shell or a non-continuous shell viaits adsorption to the active oxygen components. Beneficially, thehydrophobic particulate component provides characteristics of a powderof nanoparticle solid, until such time as the dry active oxygencomposition breaks down (e.g. by shear contact) and releases the liquidor aqueous component. In an aspect, the hydrophobic particulate shellcomponent forms an outer adsorbed layer of particulate floating on thesurface of liquid droplets for the dry powder compositions, effectivelyprotecting, stabilizing, delaying and/or controlling the release and/ordistribution of the active oxygen component contained there within, asshown in FIG. 1.

In an aspect of the invention, the hydrophobic particulate componentaccording to the invention is water insoluble. In still further aspectsof the invention, the hydrophobic particulate component is notsubstantially reactive with water.

Exemplary hydrophobic, water insoluble, solid particulates includehydrophobically-modified derivatives of silica, alumina, titanium, zinc,clay, and mixtures thereof. Preferably the hydrophobic, water insoluble,solid particulates are hydrophobically chemically-modified derivativesof silica, alumina, titanium, zinc, clay, and mixtures thereof.

Optionally, the solid particulates may be water-insoluble, solidparticulates of hydrophilic silica, alumina, titanium, zinc, clay andmixtures thereof which have been physically modified by premixing with awater-insoluble cationic compound such that the resulting particulatesare then hydrophobic in nature.

Exemplary silica for use as the hydrophobic particulate componentincludes chemically-modified silica, wherein the hydroxyl groups havebeen modified to impart hydrophobic properties. Preferably, the hydroxylgroups have been modified with a silane to increase hydrophobicity ofthe particulate. In an aspect, at least about 30% of the hydroxyl groupshave been modified with a silane, and preferably at least 50% of thehydroxyl groups have been modified with a silane.

In a preferred aspect, the hydrophobicly modified silica is also a fumedsilica. As referred to herein, fumed silica are composed of amorphous orcrystalline silicon dioxide manufactured using a combustion process toproduce silica having branched or aggregate networks of micron size(generally 20-30 μm). An example of a commercially-available, modifiedhydrophobically fumed silica is Aerosil® R812S, a fumed silica modifiedwith an organosilane to impart hydrophobicity (Evonik Industries).Preferably, the modified silica has the silanol groups (Si—OH)substituted by dimethyl-dichlorosilane and hexamethyldisilazane groups.Exemplary descriptions of the physical and chemical properties ofcertain hydrophobically modified fumed silica available from EvonikIndustries is set forth in Table 1.

TABLE 1 BET Methanol Aerosil ® Primary particle size surface Tappeddensity Substituted group Carbon content wettability R812S  7 nm 220m²/g 50 g/L

3-4% 60% R972 16 nm 110 m²/g 50 g/L

0.6-1.2% 30%

In a still further preferred aspect, the hydrophobic silica is not analkali metal silicate or other silicate component that dissolves or issuspended within the active oxygen oxidant according to the invention.Instead, the hydrophobic particulate component forms an adsorbed outerlayer around the active oxygen component.

In an aspect, the compositions include from about 0.01 wt-%-30 wt-%hydrophobic particulate component, from about 0.1 wt-%-20 wt-%hydrophobic particulate component, from about 0.1 wt-%-10 wt-%hydrophobic particulate component, preferably from about 1 wt-%-5 wt-%hydrophobic particulate component. In addition, without being limitedaccording to the invention, all ranges recited are inclusive of thenumbers defining the range and include each integer within the definedrange.

In an aspect, the ratio of hydrophobic particulate component to theactive oxygen component is from about 30:70 to about 2:98. In anotheraspect, the ratio of hydrophobic particulate component to the activeoxygen component is from about 20:80 to about 3:97, preferably fromabout 10:90 to about 5:95. Without being limited according to theinvention, all ranges recited are inclusive of the numbers defining therange and include each integer within the defined range.

In another aspect of the invention, the size of the composite dropletformed by the hydrophobic particulate component can be describedaccording to the radius of the powder. In an aspect, r is the radius ofa particle of the composite composition, assuming about equal densitiesfor the liquid droplet and adsorbed layer of hydrophobic particulate anda monolayer of adsorbed hydrophobic particulate, wherein:

${\frac{{wt}\mspace{14mu} \% \mspace{14mu} {starting}\mspace{14mu} {liquid}}{{wt}\mspace{14mu} \% \mspace{14mu} {starting}\mspace{14mu} {particulate}} \sim \frac{{volume}\mspace{14mu} {of}\mspace{14mu} {liquid}\mspace{14mu} {droplet}}{{surface}\mspace{14mu} {area}\mspace{14mu} {of}\mspace{14mu} {liquid}\mspace{14mu} {droplet}}} = {\frac{\left( {4\text{/}3} \right)({pi})r^{3}}{4({pi})r^{2}} = \frac{r}{3}}$

One skilled in the art would be able to use the above equation and bymeasuring the radius of the composite droplet develop an estimation ofthe weight ratio of the starting aqueous liquid and hydrophobicparticulate in the composite. In an aspect the r value according tocompositions of the invention is the weight ratio of the liquid activeoxygen component to the hydrophobic particulate component and is equalto the radius of a droplet of the liquid component divided by 3.

Active Oxygen Component

The compositions according to the invention include an active oxygencomponent. The active oxygen component may include any active oxygenoxidant, including for example any water soluble active oxygen oxidant.The active oxygen component selected for formulation within the drypowder compositions is combined with the hydrophobic and water insolubleshell component to form a particle or nanoparticle composite compositionthat is substantially non-reactive in combination. In an aspect, theactive oxygen component is substantially non-reactive with thehydrophobic particulate component.

Active oxygen oxidants are preferably provided as aqueous solutions ofthe active oxygen oxidant. Exemplary active oxygen oxidants includehydrogen peroxide, peroxy compounds, peroxycarboxylic acids and/orsulfonated peroxycarboxylic acids, persulfates, perborates,percarbonates, perphosphates, persilicates, other water-soluble activeoxygen oxidants, urea, and the like.

According to an embodiment of the invention suitable peroxycarboxylicacids include ester peroxycarboxylic acids, alkyl ester peroxycarboxylicacids, sulfoperoxycarboxylic acids, and/or combinations of severaldifferent peroxycarboxylic acids, as described herein. Suitable peroxycompounds include, for example, aromatic or aliphatic peroxy compounds,including peroxycarboxylic acid. Suitable peroxycarboxylic acidsinclude, for example, peracetic or peroctanoic acid, sulfonatedpercarboxylic acids, such as peroxy sulfonated oleic acid, and the like.A commercial example of a suitable active oxygen component is Oxonia®Active Concentrate, which is a mixture of peracetic acid, acetic acid,hydrogen peroxide, organophosphonate stabilizer, and water (EcolabInc.).

Peroxycarboxylic (or percarboxylic acid or peracids) refer synonymouslyto acids having the general formula R(CO₃H)_(n). The R group can besaturated or unsaturated as well as substituted or unsubstituted. Asdescribed herein, R is an alkyl, aryl alkyl, cycloalkyl, aromatic,heterocyclic, or ester group, such as an alkyl ester group. N is one,two, or three, and named by prefixing the parent acid with peroxy. Estergroups are defined as R groups including organic moieties (such as thoselisted above for R) and ester moieties. Exemplary ester groups includealiphatic ester groups, such as R₁OC(O)R₂, where each of R₁ and R₂ canbe aliphatic, preferably alkyl, groups described above for R. PreferablyR₁ and R₂ are each independently small alkyl groups, such as alkylgroups with 1 to 5 carbon atoms.

As referred to herein, peroxycarboxylic acids preferably include shortchain peroxycarboxylic acid (e.g., peroxyacetic acid) and/or mediumchain peroxycarboxylic acids (e.g., octanoic acid). Peroxycarboxylicacids useful in the compositions according to the invention include, forexample, peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic,peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic,peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic,peroxylactic, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic,peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric,peroxyadipic, peroxypimelic, peroxysubric acid, or mixtures thereof.Medium chain peroxycarboxylic acids useful in the compositions of thepresent invention include peroxypentanoic, peroxyhexanoic,peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic,peroxyundecanoic, peroxydodecanoic, peroxyascorbic, peroxyadipic,peroxycitric, peroxypimelic, or peroxysuberic acid, mixtures thereof, orthe like. Short chain peroxycarboxylic acids useful in the compositionsand methods of the present invention include peroxyformic, peroxyacetic,peroxypropionic, peroxybutanoic, peroxyoxalic, peroxymalonic,peroxysuccinic acid, mixtures thereof, or the like. The alkyl backbonesof these peroxycarboxylic acids can be straight chain, branched, or amixture thereof. Peroxy forms of carboxylic acids with more than onecarboxylate moiety can have one or more (e.g., at least one) of thecarboxyl moieties present as peroxycarboxyl moieties. Peroxycarboxylicacids can also include the ester peroxycarboxylic acids described hereinand compositions of the present invention including those esterperoxycarboxylic acids. Peroxy forms of carboxylic acids with more thanone carboxylate moiety can have one or more of the carboxyl moietiespresent as peroxycarboxyl moieties.

In some embodiments of the invention at least one sulfoperoxycarboxylicacid is employed. Sulfoperoxycarboxylic acids, also referred to hereinas sulfonated peracids, may also be used according to the invention andare understood to include the peroxycarboxylic acid form of a sulfonatedcarboxylic acid. The peroxycarboxylic acid chain can be sulfonated at avariety of locations. In some embodiments, the sulfonated peracids ofthe present invention are mid-chain sulfonated peracids, referring to aperacid compound that includes a sulfonate group attached to a carbonthat is at least one carbon (e.g., the three position or further) fromthe carbon of the percarboxylic acid group in the carbon backbone of thepercarboxylic acid chain, wherein the at least one carbon is not in theterminal position. As used herein, the term “terminal position,” refersto the carbon on the carbon backbone chain of a percarboxylic acid thatis furthest from the percarboxyl group.

According to an embodiment of the invention, sulfoperoxycarboxylic acidshave the following general formula:

wherein R₁ is hydrogen, or a substituted or unsubstituted alkyl group;R₂ is a substituted or unsubstituted alkyl group; X is hydrogen, acationic group, or an ester forming moiety; or salts or esters thereof.

In some embodiments, R₁ is a substituted or unsubstituted C_(m) alkylgroup; X is hydrogen a cationic group, or an ester forming moiety; R₂ isa substituted or unsubstituted C_(n) alkyl group; m=1 to 10; n=1 to 10;and m+n is less than 18, or salts, esters or mixtures thereof. In someembodiments, R₁ is hydrogen. In other embodiments, R₁ is a substitutedor unsubstituted alkyl group. In some embodiments, R₁ is a substitutedor unsubstituted alkyl group that does not include a cyclic alkyl group.In some embodiments, R₁ is a substituted alkyl group. In someembodiments, R₁ is an unsubstituted C₁-C₉ alkyl group. In someembodiments, R₁ is an unsubstituted C₇ or C₈ alkyl. In otherembodiments, R₁ is a substituted C₈-C₁₀ alkyl group. In someembodiments, R₁ is a substituted C₈-C₁₀ alkyl group is substituted withat least 1, or at least 2 hydroxyl groups. In still yet otherembodiments, R₁ is a substituted C₁-C₉ alkyl group. In some embodiments,R₁ is a substituted C₁-C₉ substituted alkyl group is substituted with atleast 1 SO₃H group. In other embodiments, R₁ is a C₉-C₁₀ substitutedalkyl group. In some embodiments, R₁ is a substituted C₉-C₁₀ alkyl groupwherein at least two of the carbons on the carbon backbone form aheterocyclic group. In some embodiments, the heterocyclic group is anepoxide group.

In further embodiments, R₂ is a substituted C₁-C₁₀ alkyl group. In someembodiments, R₂ is a substituted C₈-C₁₀ alkyl. In some embodiments, R₂is an unsubstituted C₆-C₉ alkyl. In other embodiments, R₂ is a C₈-C₁₀alkyl group substituted with at least one hydroxyl group. In someembodiments, R₂ is a C₁₀ alkyl group substituted with at least twohydroxyl groups. In other embodiments, R₂ is a C₉ alkyl groupsubstituted with at least one SO₃H group. In some embodiments, R₂ is asubstituted C₉ group, wherein at least two of the carbons on the carbonbackbone form a heterocyclic group. In some embodiments, theheterocyclic group is an epoxide group. In some embodiments, R₁ is aC₈-C₉ substituted or unsubstituted alkyl, and R₂ is a C₇-C₈ substitutedor unsubstituted alkyl.

Additional sulfoperoxycarboxylic acids suitable for use in the peracidcompositions of the invention include, for example, the following and/orany salts, esters and mixtures thereof:

Further description of suitable sulfoperoxycarboxylic acids, and methodsof making the same, according to the invention are included in U.S.patent application Ser. Nos. 13/290,355, 12/568,493 and 12/413,179,entitled “Sulfoperoxycarboxylic Acids, Their Preparation and Methods ofUse as Bleaching and Antimicrobial Agents,” hereby expresslyincorporated herein in its entirety by reference, including withoutlimitation all drawings and chemical structures contained therein.

In some embodiments of the invention at least one carboxylic acid isemployed in the peroxycarboxylic acid compositions due to theformulation of the dry powder compositions using an equilibriumperoxycarboxylic acid as the active oxygen oxidant. Generally,carboxylic acids have the formula R—COOH wherein the R can represent anynumber of different groups including aliphatic groups, alicyclic groups,aromatic groups, heterocyclic groups, and ester groups, such as alkylester groups, all of which can be saturated or unsaturated and/orsubstituted or unsubstituted. Carboxylic acids can have one, two, three,or more carboxyl groups. Preferred ester groups include aliphatic estergroups, such as R₁OC(O)R₂— where each of R₁ and R₂ can be aliphatic,preferably alkyl, groups described above for R. Preferably R₁ and R₂ areeach independently small alkyl groups, such as alkyl groups with 1 to 4carbon atoms.

The composition of the invention can employ carboxylic acids containingas many as 22 carbon atoms. Examples of suitable carboxylic acidsinclude formic, acetic, propionic, butanoic, pentanoic, hexanoic,heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, lactic,maleic, ascorbic, citric, hydroxyacetic (glycolic), neopentanoic,neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic,pimelic suberic, and sebacic acid. Examples of suitable alkyl estercarboxylic acids include monomethyl oxalic acid, monomethyl malonicacid, monomethyl succinic acid, monomethyl glutaric acid, monomethyladipic acid, monomethyl pimelic acid, monomethyl suberic acid, andmonomethyl sebacic acid; monoethyl oxalic acid, monoethyl malonic acid,monoethyl succinic acid, monoethyl glutaric acid, monoethyl adipic acid,monoethyl pimelic acid, monoethyl suberic acid, and monoethyl sebacicacid; monopropyl oxalic acid, monopropyl malonic acid, monopropylsuccinic acid, monopropyl glutaric acid, monopropyl adipic acid,monopropyl pimelic acid, monopropyl suberic acid, and monopropyl sebacicacid, in which propyl can be n- or isopropyl; and monobutyl oxalic acid,monobutyl malonic acid, monobutyl succinic acid, monobutyl glutaricacid, monobutyl adipic acid, monobutyl pimelic acid, monobutyl subericacid, and monobutyl sebacic acid, in which butyl can be n-, iso-, ort-butyl.

In some embodiments, the carboxylic acid for use with the compositionsof the present invention is a C₂ to C₁₂ carboxylic acid. In someembodiments, the carboxylic acid for use with the compositions of thepresent invention is a C₅ to C_(ii) carboxylic acid. In someembodiments, the carboxylic acid for use with the compositions of thepresent invention is a C₁ to C₄ carboxylic acid. Examples of suitablecarboxylic acids include, but are not limited to, formic, acetic,propionic, butanoic, pentanoic, hexanoic, heptanoic, octanoic, nonanoic,decanoic, undecanoic, dodecanoic, as well as their branched isomers,lactic, maleic, ascorbic, citric, hydroxyacetic, neopentanoic,neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic,pimelic subric acid, and mixtures thereof. Carboxylic acids that aregenerally useful include ester carboxylic acids, such as alkyl estercarboxylic acids.

The active oxygen oxidant can also include a mixture of compounds, suchas more than one peroxycarboxylic acid. As used herein, the terms“mixed” or “mixture” when used relating to “peroxycarboxylic acidcomposition” or “peroxycarboxylic acids” refer to a composition ormixture including more than one peroxycarboxylic acid, such as acomposition or mixture including peroxyacetic acid (POAA) andperoxyoctanoic acid (POAA). According to one embodiment, the compositionincludes more than one C₁-C₂₂ peroxycarboxylic acids. According to oneembodiment, the composition includes one or more small C₂-C₄peroxycarboxylic acids, one or more large C₈-C₁₂ peroxycarboxylic acids,one or more ester peroxycarboxylic acids, one or more alkyl esterperoxycarboxylic acids, and/or one or more mono- or di-peroxycarboxylicacid having up to 12 carbon atoms. According to a further embodiment,the peroxycarboxylic acid has from 2 to 12 carbon atoms. According to anembodiment, the peroxycarboxylic acids include peroxyacetic acid (POAA)(or peracetic acid having the formula CH₃COOOH) and/or peroxyoctanoicacid (POOA) (or peroctanoic acid having the formula, for example, ofn-peroxyoctanoic acid (CH₃ (CH₂)₆COOOH).

In a preferred aspect, the active oxygen oxidant is a peroxycarboxylicacid and/or sulfonated peroxycarboxylic acid. The use of these activeoxygen oxidants is distinct from various “non-dry water” applicationsusing oxygen oxidants for the subsequent in situ generation of aperoxyacid. For example, U.S. Pat. No. 7,435,714, which is hereinincorporated by reference in its entirety, discloses the use of sodiumpercarbonate as a bleaching agent for the subsequent in situ generationof a peroxyacid upon dissolution into a wash at a point of use.Beneficially, the dry active oxygen composition according to the presentinvention directly deliver peroxyacids or peroxycarboxylic acids in thedry-to-touch powder formulations without subsequent in situ generationrequired due to the formation of the stable composite powdercompositions having an adsorbed outer layer of a porous hydrophobicparticulate and an inner liquid layer of the active oxygen oxidant.

In a still further preferred aspect, the active oxygen oxidant is notsodium or other alkali metal percarbonate. Preferably, the active oxygenoxidant is an equilibrium composition of a hydrogen peroxide oxidant, aperoxycarboxylic acid and/or sulfonated peroxycarboxylic acid, and thecorresponding carboxylic acids thereof. In still further preferredaspects, the active oxygen oxidant is an equilibrium peroxycarboxylicwherein the peracid exists in equilibrium with its correspondingcarboxylic acid and the hydrogen peroxide oxidizing agent.

In some aspects, the aqueous solution of the active oxygen oxidant has apH of about 8 or less. In further aspects, the aqueous solution of theactive oxygen oxidant has a pH of about 7 or less, about 6 or less,about 5 or less or about 4 or less.

In an aspect, the compositions include from about 1 wt-%-99 wt-% activeoxygen component, from about 50 wt-%-97 wt-% active oxygen component,from about 60 wt-%-95 wt-% active oxygen component, preferably fromabout 70 wt-%-95 wt-% active oxygen component. In addition, withoutbeing limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range. As referred to herein, the weight percentagerange of the active oxygen component includes the total amount of anequilibrium formulation in the event the active oxygen component is aperoxycarboxylic acid, having an equilibrium of the peroxycarboxylicacid, carboxylic acid and the hydrogen peroxide.

In an aspect, the ratio of the active oxygen component to thehydrophobic particulate component is from about 70:30 to about 98:2. Ina further aspect, the ratio of the active oxygen component to thehydrophobic particulate component is from about 80:20 to about 97:3,preferably from about 90:10 to about 95:5. The weight ratios of the drypowder compositions according to the invention referring to the activeoxygen component include the concentration by weight of the entireaqueous liquid component of the compositions. For example, in someaspects the inner liquid phase of the compositions may further includeactive oxygen stabilizing components, water and/or additional functionalingredients as disclosed herein according to embodiments of theinvention. Without being limited according to the invention, all rangesrecited are inclusive of the numbers defining the range and include eachinteger within the defined range and when referring to the active oxygencomponents may also include the additional optional liquid or aqueouscomponents of the compositions.

Active Oxygen Stabilizers

The compositions according to the invention include an active oxygenstabilizer. The active oxygen stabilizer remains in solution or in aliquid suspension with the active oxygen component within the dry powdercompositions. Exemplary active oxygen stabilizers include organic acids,chelants or sequestrants, free radical scavengers or mixtures thereof,which provide enhanced stability of the active oxygen component and mayalso provide beneficial effects on the cleaning action of thecompositions.

Suitable active oxygen stabilizer include water-soluble organicchelating compounds that sequester metal ions in solution, particularlytransition metal ions. Such sequestrants include organic amino- orhydroxy-polyphosphonic acid complexing agents (either in acid or solublesalt forms), carboxylic acids (e.g., polymeric polycarboxylate),hydroxycarboxylic acids, or aminocarboxylic acids. A particularlysuitable organic acid for use as the active oxygen stabilizers is aceticacid.

Particularly suitable chelants for use as the active oxygen stabilizersinclude, for example, phosphates, phosphonates,diethylenetriaminepentaacetic acid (DTPA), dipicolinic acid, and thelike. The sequestrant can be or include phosphonic acid or phosphonatesalt. Suitable phosphonic acids and phosphonate salts include 1-hydroxyethylidene-1,1-diphosphonic acid (CH₃C(PO₃H₂)₂OH) (HEDP);ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; or mixtures thereof. Suitableorganic phosphonates include HEDP.

The sequestrant can be or include aminocarboxylic acid type sequestrant.Suitable aminocarboxylic acid type sequestrants include the acids oralkali metal salts thereof, e.g., amino acetates and salts thereof.Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid;hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA);ethylenediaminetetraacetic acid (EDTA);N-hydroxyethylethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof.

Particularly suitable free radical scavengers for use as thewater-soluble active oxygen stabilizers include, for example, ascorbicacid or tocopherol acetate. Additional free radical scavengers may alsoinclude antioxidants.

In some aspects, the aqueous solution of the active oxygen oxidant andthe stabilizer has a pH of about 8 or less. In further aspects, theaqueous solution of the active oxygen oxidant and the stabilizer has apH of about 7 or less, about 6 or less, about 5 or less or about 4 orless.

In an aspect, the compositions include from about 0 wt-%-25 wt-%stabilizer, from about 0.01 wt-%-25 wt-% stabilizer, from about 0.1wt-%-25 wt-% stabilizer, preferably from about 0.1 wt-%-10 wt-% activeoxygen component. In addition, without being limited according to theinvention, all ranges recited are inclusive of the numbers defining therange and include each integer within the defined range.

Additional Functional Ingredients

The components of the dry active oxygen compositions according to theinvention can further be combined with various functional componentssuitable for use in a variety of applications employing active oxygencleaning compositions. In some embodiments, the compositions includingthe active oxygen component (provided in an aqueous formulation), thehydrophobic silica component and optionally the active oxygenstabilizing component make up a large amount, or even substantially allof the total weight of the dry active oxygen compositions. For example,in some embodiments few or no additional functional ingredients aredisposed therein.

In other embodiments, additional functional ingredients may be includedin the compositions. The functional ingredients provide desiredproperties and functionalities to the active oxygen-containingcompositions. For the purpose of this application, the term “functionalingredient” includes a material that when dispersed or dissolved in thedry-to-touch powder compositions used for providing an active oxygencomposition to a point of use, provides a beneficial property in aparticular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional ingredients may be used. For example, many of thefunctional materials discussed below relate to materials used incleaning applications, specifically biocide and/or bleachingapplications. However, other embodiments may include functionalingredients for use in other applications.

In preferred embodiments, the compositions do not include surfactants.Without being limited to a particular theory of the invention,surfactants are not included with the active oxygen compounds as theyare incompatible. In an aspect the surfactants cause wetting of theadsorbed particulate layer and the subsequent collapse of the compositepowder into a liquid. In additional preferred embodiments, thecompositions do not include materials insoluble in the liquid portion ofthe composite composition. In other embodiments, the compositions mayinclude for example, catalyst, anti-redeposition agents, additionalbleaching agents, bleach activators, solubility modifiers, dispersants,metal protecting agents, stabilizing agents, corrosion inhibitors,enzymes, antimicrobial agents, sequestrants and/or chelating agents,fragrances and/or dyes, rheology modifiers or thickeners, buffers and/orpH modifiers, solvents (e.g. hydrophilic substituents for maintainingthe liquid phase within the dry powder compositions), preservatives,other polymers, water and the like.

Bleach Activators

In an aspect, the dry active oxygen compositions may be furtherformulated to include additional compositions of the hydrophobicparticulate components surrounding a droplet of an aqueous solution of ableach activator. In such an aspect, it may be desirable to have withina single composition the encapsulated bleach activators providedsimultaneously with the encapsulated active oxygen components of theinvention. In some aspects, by combining the dry active oxygencompositions with the encapsulated aqueous compositions of bleachactivators, a self-activating composition of active oxygen compositions,namely peroxycarboxylic acid compositions, are provided in a shelfstable manner.

A bleach activator enhances the bleaching performance of a peracidcomposition. Notably, as referred to herein, the bleach activator is nota compound that reacts with a hydrogen peroxide (or other oxidizingagent) to form a peracid (or the activated peroxygen bleachingcompound). Instead, the bleach activator according to the inventionenhances bleaching performance of the peracid composition itself. In anaspect, a non-metal bleaching activator is employed. In an aspect, thebleach activator is a nitrogen-containing compound, preferably apolymeric amine. In a further aspect, the bleach activator is apolymeric amine or a polyamine. Preferred polymeric amines include, forexample, polyethyleneimine compounds (PEI) and/or its derivatives.Polyethyleneimines may include primary, secondary or tertiary aminecompounds. The polyethyleneimine compounds and/or its derivatives mayinclude linear and/or branched polyethyleneimines. Still further,polyethyleneimines and/or its derivatives can vary significantly inmolecular weight, topology and shape, including for example linear,branched or comb-like structures as a result of ring-openingpolymerization of the ethylenimine. See Angelescu et al., Langmuir, 27,9961-9971 (2011), which is incorporated herein by reference in itsentirety. According to an aspect of the invention, the bleach activatormay be a linear and/or branched polyethyleneimine, additional disclosureof which is set forth in U.S. patent application Ser. No. 13/661,352,titled “Amine Salt Activation of Peroxycarboxylic Acids,” which isherein incorporated by reference in its entirety.

Suitable polyethyleneimine compounds useful in the present invention maycontain a mixture of primary, secondary, and tertiary aminesubstituents. The mixture of primary, secondary, and tertiary aminesubstituents may be in any ratio, including for example in the ratio ofabout 1:1:1 to about 1:2:1 with branching every 3 to 3.5 nitrogen atomsalong a chain segment. Alternatively, suitable polyethyleneiminecompounds may be primarily one of primary, secondary or tertiary aminesubstituents. Exemplary PEI products include multifunctional cationicpolyethyleneimines with branched polymer structures according to thefollowing formulas (—(CH₂—CH₂—NH)_(n)—), with a molecular mass of 43.07(as repeating units). In certain aspects the formula(—(CH₂—CH₂—NH)_(n)—) has a value of n that is at least 10 to 10⁵, andwherein the nitrogen to carbon ratio is 1:2. PEI polymers have thegeneral following polymer structure:

PEI products can also be represented by the following general formula,which may vary according to substitutions, size, molecular weight,branching, and the like:

(—NHCH₂CH₂—)_(x)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(y)

wherein x is an integer that is 1 or greater and y is an integer that is1 or greater than 1. Preferably, wherein x is an integer from about 1 toabout 120,000, preferably from about 2 to about 60,000, more preferablyfrom about 3 to about 24,000 and y is an integer from about 1 to about60,000, preferably from about 2 to about 30,000, more preferably fromabout 3 to about 12,000.

Various commercial polyethyleneimines are available, including forexample those sold under the tradename Lupasol® (BASF), including forexample Lupasol® FG, Lupasol® G, Lupasol® PR 8515, Lupasol® WF, Lupasol®G 20/35/100, Lupasol® HF, Lupasol® P, Lupasol® PS, Lupasol® PO 100,Lupasol® PN 50/60, and Lupasol® SK. Such exemplary polyethyleneiminesare available as anhydrous polyethyleneimines and/or modifiedpolyethyleneimines provided in aqueous solutions or methoyxypropanol(Lupasol® PO 100). The molar mass of the polyethyleneimines, includingmodified polyethyleneimines can vary from about 800 g/mol to at least2,000,000 g/mol.

In certain aspects the polymeric amine bleach activators, and preferablythe PEI bleach activators, may be a branched, spherical polymeric amine.In further aspects, the molecular weight of the polymeric amine bleachactivators or PEI bleach activators is from about 100 Daltons to about 2million Daltons (PEI-2,000,000), more preferably from about 100 Daltonsto about 1 million Daltons (PEI-1,000,000), more preferably from about500 Daltons to about 500 kDa (PEI-500,000), more preferably from about500 Daltons to about 50 kDa (PEI-50,000), more preferably from about 800Daltons to about 50 kDa (PEI-50,000), more preferably from about 800Daltons to about 10 kDa (PEI-10,000).

In further aspects, the charge density of the PEI or PEI salt is fromabout 15 mEq/g to about 25 mEq/g, more preferably from about 16 mEq/g toabout 20 mEq/g. Commercially-available examples of such preferred PEIsinclude the BASF products LUPASOL® WF (25 kDa; 16-20 mEq/g) and Lupasol®FG (800 Daltons; 16-20 mEq/g), and the BASF products in the SOKALAN®family of polymers, e.g., SOKALAN® HP20, SOKALAN® HP22 G, and the like.

In an aspect, a polymeric amine may contain other substituents and/orand copolymers. For example, a polymeric amine may also includesubstituents, including for example ethoxylates and propoxylates. In anaspect of the invention, the polymeric amine, such as apolyethyleneimines, are derivatized with ethylene oxide (EO) and/orpropylene oxide (PO) side chains. In an exemplary aspect of theinvention ethoxylated PEIs may be heavily branched, wherein thesubstitutable hydrogens on the primary and secondary nitrogens arereplaced with ethoxylated chains containing varying degrees of repeatingunits. In an aspect, the bleach activator is a polyethyleneimine polymerwith ethyleneoxide chains. Ethoxylation of PEIs increases the solubilityof the bleach activator according to the invention. A polymeric aminemay also include endcap substituents, including for exampleethylenediamine. A variety of substituents and/or copolymers may beincluded in order to modify the solubility or any other physicalcharacteristics of a particular polymeric amine employed as a bleachactivator according to the invention.

Because of the presence of amine groups, PEI can be protonated withacids to form a PEI salt from the surrounding medium resulting in aproduct that is partially or fully ionized depending on pH. For example,about 73% of PEI is protonated at pH 2, about 50% of PEI is protonatedat pH 4, about 33% of PEI is protonated at pH 5, about 25% of PEI isprotonated at pH 8 and about 4% of PEI is protonated at pH 10. Ingeneral, PEIs can be purchased as their protonated or unprotonated formwith and without water. The counter ion of each protonated nitrogencenter is balanced with an anion of an acid obtained duringneutralization. Examples of protonated PEI salts include, but are notlimited to, PEI-hydrochloride salt, PEI-sulfuric acid salt, PEI-nitricacid salt, PEI-acetic acid salt PEI fatty acid salt and the like. Infact, any acid can be used to protonate PEIs resulting in the formationof the corresponding PEI salt compound.

Embodiments

Exemplary ranges of preferred components of the dry-to-touch activeoxygen powder compositions according to the invention are shown in Table2 in weight percentage of the powder compositions encapsulating theaqueous or liquid-containing active oxygen component.

TABLE 2 First Second Third Fourth Exemplary Exemplary ExemplaryExemplary Material Range wt-% Range wt-% Range wt-% Range wt-%Hydrophobic 0.1-30  1-20  1-10  1-5 Silica Component Active Oxygen50-99  60-97   70-95  80-95 Component Active Oxygen 0-25 0.01-25  0.1-25 0.1-10 Stabilizing Component Additional 0-50 0-30 0.01-30  0.1-25Functional Ingredients

In an aspect the active oxygen component may include a varying amount ofwater and/or other solvents. In an aspect, the active oxygen componentincludes from about 0 wt-% to about 70 wt-% water, preferably from about0.1 wt-% to about 40 wt-%, from about 1 wt-% to about 30 wt-%, or fromabout 2 wt-% to about 20 wt-% water.

According to an aspect of the invention, the dry active oxygencompositions may include a single active oxygen component surrounded bythe dry powder composite compositions. In a further embodiment, the dryactive oxygen compositions may include a plurality of active oxygencomponents surrounded by the dry powder composite compositions. In stillfurther aspects, the dry-to-touch powder compositions may employ asingle type of adsorbed particulate component (i.e. hydrophobic shellcomponent) or a plurality of adsorbed particulates. Beneficially, thedry powders delivering active oxygen compounds are low or no odorcompositions.

According to a further aspect, the dry active oxygen compositionsprovide a stable active oxygen oxidant. The term “stable” as appliedherein to an active oxygen oxidant within the dry powder compositionsaccording to the invention means a composition that retains at leastabout 90% of the active oxygen oxidant for at least about 6 months in asealed container, or that retains at least about 90% of the activeoxygen oxidant for at least about 3 months in a sealed container. In anaspect, composition may have improved stability within a sealedcontainer having a venting device as a safety feature.

The compositions enable the formulation of concentrated active oxygencompounds. Beneficially, due to the adsorbed outer composite structureof the compositions the need for personal protective equipment for thosehandling the compositions is reduced. The compositions also provide theformulation of unit dose delivery, which may be applied to a surface orarticle in need of treatment and a remainder of the compositions may bestored in a sealed container for prolonged stability.

Kits

The dry active oxygen compositions may be provided in the form of a kit.In an aspect, a kit may comprise, consist of and/or consist essentiallyof a sealed container (with or without a venting feature for improvedsafety), the dry active oxygen compositions according to the invention,and instructions for application of use.

The kits can further include the components for treating the surfacesand/or articles disclosed in the methods of using the compositions. Inan aspect, the instructions for how to use the compositions includeinstructions for treating the surfaces and/or articles. In some aspects,the kits are especially suited for consumer use.

Methods of Making

The dry active oxygen compositions according to the invention may bemade by combining the liquid or aqueous active oxygen componentcomposition with the hydrophobic particulate component under low,medium, or high shear mixing conditions. High shear mixing may furtherinclude vigorous agitation of the liquid or aqueous components with thehydrophobic shell component for a sufficient amount of time to form thedry-to-touch powder compositions. In some aspects, the shear mixing oragitation is required for a period of time from about a few minutes toat least an hour.

In an aspect, high shear mixing conditions are referred to herein toinclude, for example, the use of rotor or impellor, often with the useof a stationary component (e.g. stator or an array of rotors andstators) with are used within a tank or container with the liquidcomponent to be mixed, or using other configurations as one skilled inthe art is familiar with to create various emulsions, suspensions,lyosols and/or granular products.

Additional aspects of the methods of making the dry active oxygencompositions are disclosed for example in the treatment of hydrophobicparticles for an adsorbed outer layer using vigorous agitation oraerosolization of a solution in the presence of the hydrophobicparticles to form a solid powder, such as described in U.S. Pat. Nos.7,030,071, 6,716,885, 5,342,597, 4,008,170 and 3,393,155, and by Formyet al., Powder Technology 171 (2007) 15-24, which are hereinincorporated by reference in their entirety.

In an aspect, the use of high shear mixing (or other method) of a liquidactive oxygen component (e.g. peroxyacid composition) in the presence ofthe hydrophobic adsorbed particulate component (e.g. fumed silicamodified with hydrophobic components) in approximately a 98:2 weightratio to about 80:20 weight ratio, a dry powder composition having aliquid active oxygen component disposed therein can is formed. In anaspect, the hydrophobic shell component (e.g. silica) forms a layer ofadsorbed insoluble fine particles or nanoparticles floating on thesurface of a the liquid portion (e.g. solution of an equilibriumperoxyacid composition). Alternatively, other hydrophobic particles ornanoparticles (e.g. alumina or clays, as disclosed according to thecompositions) and/or other active oxygen components can be usedaccording to the methods of the invention to form composite activeoxygen compositions in the form of dry-to-touch, free flowing powders.

In an alternative aspect, the dry active oxygen compositions accordingto the invention may be made by aerosolization and/or fluidized bedspray for the outer adsorbed coating with the hydrophobic particulatecomponent. As one skilled in the art will ascertain, methods of sprayingor atomizing a liquid and a particulate stream together into air couldbe used to form the composite compositions.

In a further aspect of the invention, the methods of making the dryactive oxygen compositions may further include the step of maintainingthe encapsulated active oxygen components in a substantiallynon-reactive state. For example, according to the invention, the dryactive oxygen compositions may be maintained at ambient temperatures,low humidity, etc. to prevent the dissolution of the hydrophobicadsorbed component into the aqueous or liquid phase of the composition.Further, according to the invention, the composite composition might beplaced into contact with a glass surface to begin dispensing of theinterior liquid by destabilizing the composite.

Beneficially, according to aspects of the invention, the dry activeoxygen compositions according to the invention may be either stored in asealed container or vented container or applied for a particular methodof use according to the invention. In an aspect, the dry active oxygencompositions have a shelf-stability of at least about 2 to 6 monthswithin a sealed container, preferably at least about 6 to 12 monthswithin a sealed container. In another aspect, the dry active oxygencompositions applied to a surface in need of treatment have a stabilityof at least a few hours to at least a few days, preferably at least afew days to a few weeks, and more preferably at least a few monthsbefore the powder compositions break apart when rubbed or contactedagainst a surface to release the active oxygen component.

Methods of Use

The dry active oxygen compositions according to the invention may beemployed to deliver active oxygen compounds for a variety ofapplications of use, including cleaning, disinfecting and/or sanitizingsurfaces. Beneficially, the aqueous solution of an active oxygencomponent (e.g. bleach or an equilibrium peracid such as peracetic acidcompositions) is surrounded by an undissolved particulate shell allowingfor the aqueous solution to be delivered in a dry format, which may bereferred to as a liquid powder. The particles do not release the activeoxygen component until they are disrupted, allowing for the carefulcontrol of where the compositions are applied to prevent damage tosensitive areas and/or preclude the need for using personal protectiveequipment for persons handling concentrated compositions of the activeoxygen component.

Delivery of the dry active oxygen compositions according to theinvention may include a variety of low-pressure application techniques,using a variety of equipment known to those of skill in the art. In afurther aspect of the invention, the delivery of the dry active oxygencompositions may include the spraying of the compositions onto a surfacein need of treatment. In a further aspect of the invention, the deliveryof the dry active oxygen compositions may include the spreading (withoutmechanical force, e.g. distributing or sprinkling the dry powdercompositions over a surface). In a still further aspect, the delivery ofthe dry active oxygen compositions may include contact with a glasssurface to begin dispensing of the interior liquid by destabilizing thecomposite.

Beneficially, according to aspects of the invention, the methods ofusing the dry active oxygen compositions minimize and/or do not requirethe use of personal protective equipment due to the encapsulation of theactive oxygen component (e.g. bleach). As a further benefit, the methodsof using the dry active oxygen compositions include the administrationand use of a low or no odor compositions.

In some aspects, the dry active oxygen compositions are delivered to apoint of use for example: concrete treatment, clothes dryer additive,pesticide delivery, point of use cleaning and/or disinfecting, deliveryof composite with thickeners for various applications of use, lubricantfor bottles/cans, hydrogen peroxide encapsulate for solids, desiccantfor pest control, dry cleaning around electrical surfaces, eliminatespray boom in powder mixing in manufacturing setting, exterior buildingcleaning, fumigation alternative, bedbug treatment, fire retardant,composites of inorganic acids such as sulfuric acid for applications ofuse thereof, floor sweeping agent, carpet treatment, crop treatment, dryfloor stripper, paper additive, ester-based solvents coating, ice melt,hide incompatible ingredients from each other, control coefficient offriction on floor, etc.

In an aspect, the dry active oxygen compositions are delivered to one ormore of a variety of production facilities where an active oxygenoxidant, such as a peroxycarboxylic acid, might be used. Sites of useinclude, for example, a beverage plant, a food processing plant, adisassembly plant, a meat processing plant, wood pulp producing or paperplant, or the like. At the site of use, the dry active oxygencompositions can be applied to objects including equipment, containers,pulp, waste, and food products.

In an aspect, the dry active oxygen compositions may be dispersed orotherwise reacted with one or a plurality of reactants or othermaterials causing or promoting the disintegration of the of the adsorbedhydrophobic particulate component into the aqueous or liquid phase ofthe composition.

In another aspect, upon delivery of the dry active oxygen compositionsto a treatment zone according to the invention, the compositions willeither slowly break down due to the dispersion of the silica componentinto the aqueous liquid portion of the composition. In the alternative,mechanical or other force applied to the dry powder compositions cancause the silica component to disperse into the aqueous liquid portionof the composition or treatment zone, thereby making the active oxygencomponent available for the particular application of use. In someaspects, examples of force applied to the dry active oxygen compositionsto liberate the liquid portion of the composition containing the activeoxygen component for use, include for example, contact (e.g. personstepping on the compositions or otherwise touching the compositions),sharp force, pressure, rubbing and the like.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

A peracetic acid composition was evaluated under both low and high shearmixing conditions to evaluate the impact on mixing conditions employedfor dry water technologies using active oxygen oxidants. The comparisonof low and high shear mixing conditions were used to determine thecompatibility of the active oxygen oxidants under various formationconditions. A Warring blender was charged with 50 grams deionized water,50 grams Oxonia Active Concentrate, and 5 grams Aerosil R812S. TheOxonia Active Concentrate is a commercially available liquid mixture ofperacetic acid, acetic acid, hydrogen peroxide, organophosphonate, andwater (Ecolab Inc.). The Aerosil R812S is a commercially availablehydrophobically modified silica (Evonik Industries).

The composition tested under high shear mixing conditions was blendedfor 1 minute using the high shear mixing (blender set on ‘high’ settingand ‘liquefy’). The mixture formed a dry-to-touch powder. The powderformed was a flowable powder composition. The compositions retained suchflowable characteristic as a result of the liquid components of thecomposite remaining in aqueous solution and surrounded by an adsorbedouter layer of the hydrophobic silica.

The composition tested under low shear mixing conditions was mixed byhand for a few minutes to simulate low shear mixing. The active oxygencomposition when mixed well by hand (e.g. low shear) did not form a drypowder. Instead, the composition remained a mixture of the startingmaterials in their original state.

Example 2

A phosphonate-stabilized hydrogen peroxide composition was furtherevaluated for stability in formulating dry powder compositions accordingto the invention. A beaker was charged with 95 grams of hydrogenperoxide (35% dilution) stabilized with a phosphonate, and 5 gramsAerosil R812S. The hydrogen peroxide was employed as the active oxygenoxidant in place of the Oxonia Active Concentrate employed in Example 1.The Aerosil R812S is a commercially available hydrophobically modifiedsilica (Evonik Industries).

The composition tested under high shear mixing conditions was blendedfor 1 minute and again formed a dry-to-touch powder that was a flowablepowder composition. The substitution of the stabilized hydrogen peroxideprovides a further example of an active oxygen oxidant that is capableof remaining as a liquid component surrounded by an adsorbed outer layerof the modified, hydrophobic silica.

The compositions were then held on a hand to determine the amount ofcontact time required before a change in composition (e.g. dry-to-touchpowder back to liquid) was observed. The resulting dry powder containingthe stabilized hydrogen peroxide did not bleach the skin for up to 30minutes (demonstrating the stability of the composition and the veryslow evaporation of the encapsulating hydrophobic silica surrounding thehydrogen peroxide over time). However, rubbing the dry-to-touch powdercomposition on the skin “activated” it, resulting in a bleaching timesimilar to that of liquid hydrogen peroxide (35%) alone, from betweenabout 1-2 minutes. Beneficially, the formation of the dry-to-touchpowder prevents the active oxygen oxidant from being activated for aperiod of time, enabling the storage of the compositions in sealedcontainers for extended periods of time to prevent the evaporation ofthe encapsulating silica or other agent. Thereafter an extended periodof storage in a sealed container, the active oxygen containingcompositions can be applied for a particular use to deliver the oxidantto a particular application of use and/or time for application.

Example 3

The dry-to-touch powder compositions generated in Example 2 were furtheranalyzed for stability of the active oxidant. The compositions weretitrated initially and 24 hours later, giving nearly the same resultingamount of hydrogen peroxide concentration in the untreated liquidcomposition (35%) and the dry-to-touch powder composition (31%).

Notably, these results demonstrate a significant improvement in theretained oxidant concentration in the compositions formulated accordingto the invention, in comparison to the prior art, such as that reportedin U.S. Patent Publication No. 2003/0160209, which is hereinincorporated by reference in its entirety. The work of Hoffman et al.indicate that high concentrations of hydrogen peroxide requirepreparation immediately before use due to their instability; prior artcompositions formulated using high concentrations of hydrogen peroxidedemonstrated decomposition generating oxygen, requiring the formulationimmediately prior to use. Such limitations were not required using theformulations according to the present invention.

Example 4

The thermostability of the dry-to-touch powder compositions according toexemplary embodiments of the invention were analyzed. A TGA Q500 wasused to measure % weight lost from a sample over increasingtemperatures, as shown in FIGS. 2 and 4, according to methods known inthe art. A DSC Q200 was used to measure enthalpy changes as changes inheat flow (W/g) over increasing temperatures, as shown in FIG. 3.

FIG. 2 is a TGA for a dry powder formulation wherein the hydrophobicsilica particulate component adsorbs to an outer layer of the liquidwater phase (95 grams water and 5 grams fumed hydrophobic silica). FIG.2 shows that when the powder composition was heated to about 96° C.approximately 95% of the sample weight was lost from the composition,corresponding closely with the theoretical level of 95% water present.This shows that the water component of the dry powder system is almostcompletely evaporated near the expected boiling point for water.

FIG. 4 is also a TGA for a dry powder formulation wherein thehydrophobic silica particulate component adsorbs to an outer layer of aliquid 50% active hydrogen peroxide aqueous phase (95 grams 50% hydrogenperoxide and 5 grams fumed hydrophobic silica). FIG. 4 shows about thetheoretical level of weight loss corresponding to water loss as in FIG.2 but surprisingly does not show a corresponding loss of the higherboiling hydrogen peroxide component.

FIG. 3 is a DSC of the same material as in FIG. 4. FIG. 3 shows anendothermic event occurring near 167° C. of unknown cause butunexpectedly did not show the expected exothermic decomposition ofhydrogen peroxide over the range of test conditions, showing thehydrogen peroxide to be in a stabilized form.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims.

1. A dry active oxygen composition comprising: from about 50 wt.-% toabout 99 wt.-% of a liquid aqueous active oxygen component having a pHof less than 8, wherein said active oxygen component is an aqueoussolution of peroxycarboxylic acid, sulfonated peroxycarboxylic acid,hydrogen peroxide, persulfates, perborates, percarbonates, urea, orcombinations thereof; and from about 0.1 wt.-% to about 30 wt-% of ahydrophobic particulate component adsorbed as an outer layer surroundingsaid liquid active oxygen component, wherein said composition is aflowable, dry-to-touch powder composition by formation of a composite ofthe liquid aqueous active oxygen component and the hydrophobicparticulate component, wherein said hydrophobic particulate is adsorbedand not encapsulating onto the liquid aqueous active oxygen component,and wherein said hydrophobic particulate component does not dissolvewithin the liquid component for a period of time greater than at least24 hours.
 2. The composition of claim 1, wherein said active oxygencomponent is an aqueous solution of peroxycarboxylic acid, a sulfonatedperoxycarhoxylic acid, and/or hydrogen peroxide.
 3. The composition ofclaim 1, wherein said active oxygen component is an aqueous solution ofan equilibrium peroxycarboxylic acid and/or sulfonated peroxycarhoxylicacid.
 4. The composition of claim 1, wherein said active oxygencomponent has a pH of less than
 7. 5. The composition of claim 1,wherein said hydrophobic component is a silica.
 6. The composition ofclaim 5, wherein said silica component is not an alkali metal silicate,and wherein said silica component is a hydrophobically modified silicahaving at least about 30% of the hydroxyl groups of said silica modifiedwith a silane to increase hydrophobicity.
 7. The composition of claim 1,wherein the weight ratio of the liquid active oxygen component to thehydrophobic particulate component is about the radius of a droplet ofthe liquid component measured in μm divided by
 3. 8. The composition ofclaim 1, wherein the ratio of said active oxygen component to saidhydrophobic component is from about 80:20 to about 97:3.
 9. Thecomposition of claim 1, wherein the ratio of said active oxygencomponent to said hydrophobic component is from about 90:10 to about95:5.
 10. The composition of claim 8, wherein said composition furthercomprises an active oxygen stabilizing component selected from the groupconsisting of an organic acid, chelant, sequestrant and free radicalscavenger, and/or further comprises an additional functional ingredientin the liquid component of the composition.
 11. The composition of claim1, wherein said composition remains stable in a sealed container for atleast 6 months.
 12. The composition of claim 1, wherein said compositionfurther comprises a dry bleach activator composition comprising ahydrophobic component adsorbed as an outer layer surrounding an aqueous,non-metal bleach activator.
 13. A kit comprising: a sealed container; acomposite dry active oxygen composition comprising a liquid aqueouscomposition containing from about 50 wt-% to about 99 wt-% of an activeoxygen component having a of less than 8, wherein said active oxygencomponent is an aqueous solution of peroxycarboxylic acid, sulfonatedperoxycarboxylic acid, hydrogen peroxide, persulfates, perborates,percarbonates, urea, or combinations thereof, and from about 0.1 wt-% toabout 30 wt-% of a hydrophobic particulate component adsorbed as anouter layer surrounding said active oxygen component, wherein saidcomposition is a flowable, dry-to-touch powder composition by formationof a composite of the liquid aqueous active oxygen component and thehydrophobic particulate component, wherein said hydrophobic particulateis adsorbed and not encapsulating onto the liquid aqueous active oxygencomponent, and wherein said hydrophobic particulate component does notdissolve within the liquid component for a period of time greater thanat least 24 hours; and instructions for application of use.
 14. The kitof claim 13, wherein the dry active oxygen composition further comprisesa dry bleach activator composition comprising a hydrophobic particulatecomponent adsorbed as an outer layer surrounding liquid aqueous bleachactivator, wherein said bleach activator is a polymeric amine or apolyamine.
 15. The kit of claim 13, wherein said dry active oxygencomposition remains stable in said sealed container for at least 6months.
 16. A method of using a dry active oxygen compositioncomprising: combining a liquid aqueous active oxygen component and anadsorbed hydrophobic particulate component to form a composite dryactive oxygen composition, wherein said active oxygen component is anaqueous solution of peroxycarboxylic acid, sulfonated peroxycarboxylicacid, hydrogen peroxide, persulfates, perborates, percarbonates, urea,or combinations thereof, constitutes from about 50 wt-% to about 99 wt-%of the composition, and has a pH of less than 8, wherein saidhydrophobic particulate component constitutes from about 0.1 wt-% toabout 30 wt-% of the composition, wherein said active oxygen componentis contained within said adsorbed layer of hydrophobic particulatecomponent, wherein said composition is a flowable, dry-to-touch powder,wherein said hydrophobic particulate component does not dissolve withinthe liquid component for a period of time greater than at least 24hours; and applying said composite thy active oxygen composition to asurface in need of treatment thereof; and/or storing said composite dryactive oxygen composition within a sealed container for subsequentapplication to a surface in need of treatment.
 17. The method of claim16, wherein said composition does not dissolve into a liquid compositionupon applying to said surface for at least 24 hours.
 18. The method ofclaim 16, wherein said composition remains stable within said sealedcontainer for at least about 6 months.
 19. The method of claim 16,wherein said hydrophobic particulate component is dispersed into saidactive oxygen component upon a shear force contacting said composition.20. The method of claim 16, wherein said hydrophobic particulatecomponent is a hydrophobically modified silica having at least about 30%of the hydroxyl groups of said silica modified with a silane to increasehydrophobicity, and wherein the ratio of said active oxygen component tosaid hydrophobic component is from about 80:20 to about 97:3.